Process for resolving petroleum emulsions



Patented Emily 3%,, i3

' mtmiii iraocnss nan assonvme rn'rnonnmr EMULSHONS T/i'elvin De Groote,University City, M0,, assignor,

by mesne assignments, to Petrolite Corporation, Ltd, a corporation areDelaware Nip-namin Application May 31, 1938,:

"Serial No. aims-z, 1: I,

. *7 Claims; This invention relates to the treatment of emulsions ofmineral oil and water, such as petroleum emulsions, and has for itsobject to provide a novel process for resolving or breaking petroleumemulsions of the wat r-in-oil type into their component parts of oil andwater or brine.

The treating agent or demulsifying agent employed in the present processis a new composition of matter consisting of a certain kind of complexamine derived "by reaction between (a) acid esters obtained by reactionbetween phth-alated triricinolein, phthalated ricinoleic acid, orsimilar materials; and (b) simpler amines of the kind hereinafterdescribed, and the process involves subjecting a petroleum emulsion ofthe water-in-oil type to the action of said demulsifying agent, so as tocause the emulsion to break down and separate into its component partsof oil and water or brine when the emulsion is permitted to remain in aquiescent state after treatment or is subjected to other equivalentseparatory procedures.

Inasmuch as the demulsifying agent employed in my process constitutes anew chemical compound or new composition of matter, I deem it advisableto describe the raw materials entering into the manufacture of the same,as well as the method of manufacture. One can obtain or manufacturechemical compounds whose composition is indicated by the followingformulas:

onoin OH.C:H4-NH onc m acoocm,

nooocnn-N 3.0 O O.C2H4

The compounds above described may be summarized by the followingformula:

in which m represents the number 1 or 2, m represents the number 1 or 2,and m" represents the number or 1, with the proviso that However, theradical C2114 which appears in the above formula may represent anysimilar radical, such as a CsHc radical, C4Ha radical, etc., andtherefore the above formula may be.

rewritten:

' (R.c0o.c.Ha)e

N T fill (OH'CIIHZIJN where n represents a small whole number,preferably not over 10.

In the above group, T represents a hydrogen atom or a non-hydroxyaliphatic hydrocarbon radical, such as a methyl, ethyl, propyl, amyl, orsimilar radical; or T may represent a non-hydroxy alicyclic radical,such as a cyclohexyl radical, or a non-hydroxy aralkyl radical, such asa benzyl radical; or the acyla-ted radical obtained by replacing ahydrogen atom of the hydroxyl group of an alkylol radical by the acylradical of a monobasic carboxy acid, such as acetic acid; butyric acid,heptoic acid, or the like, all of which are characterized by having lessthan 8 carbon atoms. The alkylol radical prior to acylaticn may be ahydroxy alicyclic or a hydroxy aralkyl radical, provided that thehydroxy radical is attached to the aliphatic residue of the aralkylradical.

In the above formula, R.COO represents the oxy-acyl or acid radicalderived from the acid R.COOH. R.COOH represents any monobasicdetergent-fuming carboxy acid, such as a typical fatty acid or abieticacid or naphthenic acid. Typical fatty acids are those which; occur innaturally-occurring oils and fats and generally have eight or morecarbon atoms and not over 32 carbon atoms. Common examples include oleicacid,-stearic acid, linoleic acid, linolenic acid, ricinoleic acid,erucic acid, palmitic acid, myristlo acid, etc. These acids combine withalkali to produce soap or soap-like materials and are commonly referredto as being monobasic detergentiorming carboxy acids. Blown oils(oxidized oils) are not included. 1

The alk'ylol radical previously referred to prior to esteriflcation maybe a hydroxy alicyclic or a such as the glyceride, and a correspondingamine. This may be illustrated in the following manner:

Reference is made to copending application for patent, Ser. No. 180,993,filed December 21, 1937,

by Melvin De Groote, Bernhard Keiser, and

However, if maximum yields are not necessary, one need not resort toreactions of the kind pre- .viously described to produce secondaryamines,

but one may employ the following type of reaction:

orrom.

p.000 orroin. acoomm a.ooo-cim+ NIH- 3 newsman). a cue on.o,momohi.

NH OH.C|H4/ Suitable primary and secondary amines which may be employedto produce materials of the kind above described include the following:diethanolamine, monoethanolamine, ethyl ethanolamine, methylethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc.Qther examples include cyclohexylolamine, dicyclohexylolamine,cyclohexyl ethanolamlne, .cyclohexyl propanolamine,- benzylethanolamine,benzylpropanolamine, pentanolamine, hexanolamine, octylethanolamine,octadecylethanolamine. cyclohexanolethanolamine, etc.

Similarly, suitable tertiary mine: which may CiHa CIHi H Such amines mayserve as functional equivalents of the previously described amines andwhich are free from an ether linkage.

All of the amines of thelklnd above described and characterized by theformula:

N(T) II 011.0. a)... in which m represents the number 1 or 2, mrepresents the number 1 or 2, and m" represents the number 0. or 1, withthe proviso that m+m'.+m"=3; and n represents a small whole number,preferably not over 10, have'four common characteristics. In the firstplace, these amines are not quaternary ammonium bases or salts thereof.The expression "quaternary ammonium" is properly and conventionallyapplied to compounds in which all four hydrogen atoms of the ammoniumradical NH; have been replaced by a hydrocarbon radical oroxy-hydrocarbon radical, as, for example, in trimethyl phenyl ammoniumhydroxide.

Secondly, an important characteristic which must be recognized is thatthese amine com-v pounds are not amides. It is 'to be noted that anamide formation involves a product in which there is a direct linkagebetween the carboxylic carbon atom and the nitrogen atom in the amine.This is not the case in the compounds employed as intermediate rawmaterials for production of the compounds used as demulsifying agents inthe present process.

In the third place, it must be recognized that these compounds arederived only from basic amines. The word basic" is employed to excludeamines having little or no basicity such as the ordinary aromatic aminesor any amine having at least one aryl radical directly joined to theamino nitrogen atom. For this reason, these amine products which areherein contemplated as demulsifying agents in the resolution ofpetroleum emulsions and which necessarily are' characterized by freedomfrom any aryl groups as such, cannot be derived from aryl amines. Theyare derived solely from alkyl, alicyclic, or aralkyl amines having atleast one hydroxyl group present. It is true that in the aralkylaminesthere is an aryl group present, but it is not directly attached to thenitrogen atom as in the case of aryl amines out in fact representsnothing more or less than a substituted alkylamine. For instance, Iconsider benzylamine as being the primary-amine, phenmethyl amine.

Finally, it must be recognized that these materials have not lost anybasicity in the forms of the esterified amine and that they exhibit allthe properties of a basic amine, that is, they combine with water toform a base presumably a substituted ammonium compound, but notquaternary ammonium compound insoiar that there are always one, two orthree unsubstituted hydrogen atoms of the ammonium radical present. Theycombine with various acids to form salts. For example, they may becombined with acetic acid, hydrochloric acid, lactic acid, chloraceticacid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or anysuitable organic or inorganic acid, to form salts. It is understood thatthe reference in the specification and appended claims to the aminesincludes the basic form and the acid salts as well as the aminesthemselves. The characteristic demulsifying properties of the newcompositidns of matter herein described are contributed in part by theamine, and it is immaterial whether the amine may be considered as beingin any one of the following forms:

in which. T represents the substituents for the amino hydrogen atoms ofthe parent ammonia from which all amines are hypothetically derived andX simply represents the acid radical of any acid employed. Thisstatement applies with equal force and eflect to the final product, orcomposition of matter, which is also a basic amine of a more complextype.

Reference is again made to the formula which summarizes the variousamines used as intermediate raw materials, via:

(R.C O 0.0 "Had N(T)m" in which the characters have their previoussignificance.

Attention is directed to the fact that where the substituted alkylradical OH.R.COO,.C2H4 appears, a suitable non-aryl radical other thanan aliphatic residue may serve as the functional equivalent; forinstance, an alicyclic radical derived from a cyclohexyl radical or anaralkyl radical derived from a benzyl radical. In other words, in thehereto appended claims reference to the CnH2n radical as such or as analkylradical or residue is intended in the broad sense to include thealicyclic radicals or residues or the aralkyl radicals or residues whichare the equivalent thereof. There is no intention to include an aromaticradical where there is a direct linkage between the aromatic nucleus andthe amino hydrogen atom for the reason that such products have littleor. no basicity and do not have the characteristic properties of theamines previously described.

In indicating the-various hydroxylated tertiary amines of the non-aryltype which may be employed to produce the amine contemplated as thedemulsifying agent of the present process, it

is desirable to indicate that amines of the type where a hydroxyl acylradical replaces a hydrogen atom of the hydroxyl radical of the hydroxytertiary amine, are not included withinv the broad class of hydroxytertiary amines unless there is another lrvdroxyl radical attached tothe usual alkyl radical. For instance, if ethyl diethanolamine istreated with two moles of lactic acid so as to form the dilactylcompound of the following formula:

on o CH3CH.c-o-C2H4 on o then it is understood that such materials wouldnot represent a hydroxy tertiary amine within the meaning or scope asherein employed. If, on the other hand, triethanolamine were treatedwith lactic acid so as to give monolactyl triethanol-- amine of thefollowing composition:

omono-o-cm.

OHC H4-N OHCzlI;

Similarly, in indicating the, various hydroxylat-" ed primary orsecondary amines of the non-aryl type which may be employed to producethe amine contemplated as the demulsifying agent of the present process,it is desirable to indicate that amines of the type where a hydroxy acylradical replaces a hydrogen atom of the hydroxyl radical of a hydroxyprimary or secondaryamine, are not included within the broad class ofhydroxy tertiary amines unless there is another hydroxyl radicalattached to the usual alkyl' radical. For instance, if ethanolamine istreated with lactic acid so as to form the lactyl derivative of thefollowing formula:

' then it is understood that such materials would not represent ahydroxy primary amine within the meaning or scope as herein employed.The same would be true if the corresponding product derived fromdiethanolamine, provided that both hydroxy radicals had been esterifledwith lactic acid The manufacture of compounds from tertiary amines isrelatively simple, because no precautions are necessary to preventamidiiication. The selected detergent-forming acid, or ester, as, forexample, a fatty oil and the selected hydroxy tertiary amines, are mixedin suitable propor tions and heated at some pointabove the boiling pointof water, for instance, 110 C., and at a point below the decompositionpoint of the amine or the fatty oil, for instance, 180 (1.. for asuitable period of time, such as two to eight hours. Mild agitation isemployed. A catalyst, such as sodium oleate, sodium carbonate, causticsoda, etc., may be present in amounts of about one-half of 1% or less.It is noted that the fatty acids are employed in this instance in theform of an ester, to wit, the glyceride, although as previously pointedout, other functional equivalents can be readily employed with equalfacility. It is to be noted that the reactions above described do nottake place to any appreciable extent if the fatty acid has beenconverted into the soap or salt. Such salts'are not functionalequivalents. As previously indicated, an ester of abietic acid might beemployed, if desired.

when, however, one is employing a hydroxy secondary amine,precautions'must be taken so that one gets a'substantial percentage ofproducts derived by esteriflcation, rather than amidification. Anysuitable ester may be employed, but it is often most convenient toemploy the glyceride of a fatty acid, for instance, triricinoleln.

The selected glyceride and the selected hydroxy secondary amine aremixed in suitable proportions and heated at some point above the boilingpoint of the amine or fatty material, for

instance, 180 0., for a suitable period of time,

such as 4-24 hours. Mild agitation is employed. A catalyst, such assodium oleate, sodium carbonate, caustic soda, etc., may be present inamounts of about /2% or less. It is to be noted that the fattyacids arepreesnt in ester form and not in the form of the free acid, and thusthere is no tendency to form the salt to any marked extent, and ifconducted at the lower range of reaction temperatures, there is adecided tendency to form the esteriflcation products, rather than theamidiflcation products.

In order to illustrate suitable examples of the amines which may be usedas intermediate raw materials, the following xamples are given!Intermediate amine-Example 1 Intermediate amine-Example 2 The sameprocedure is followed as in Intermediate amine-Example 1, except thatthe ratio the manner previously described with one employed is two molesof the castor oil to three moles of triethanolamine.

Intermediate amineE:cample 3 One mole of methyl naphthenate is reactedin mole of triethanolamine.

Intermediate amine-Example l Diethanolamine is substituted fortriethanolamine in Example 3.

Intermediate amineExample 5 Methyl abietate is substtiuted for methylnaphthenate in Examples 3 and 4 above.

Intermediate amine-Example 6 Olive oil is substituted for castor oil in'Examples 1 and 2 above.

Intermediate aminc Ezample 7 Ethyl diethanolamine is substituted fortriethanoiamine in previous examples where triethanoiamine has beenemployed, but ratios changed, if required,'so that there is always onenon-esterified ethanol radical present.

Intermediate amineExample 8 cyclohexyl diethanolamine is substituted fortriethanolamine in previous examples where triethanolamine has beenemployed, but subject to the same modification'as indicated in Example 7immediately preceding.

Intermediate amineEa:ample 9 Benzyl diethanolamine is substituted fortriethanolamine in previous examples where it has been employed. (Seemodification noted in Examples 7 and.8 immediately above.)

Having prepared the relatively simpler intermediate amine of the kindpreviously described, the second step in the preparation of the newcomposition of matter is to produce acid esters of the kind obtainableby reaction between polybasic carboxy acids, or their functionalequivalents, such as the anhydrides, and hydroxylated fatty acids,esters, or the like.

The manufacture of this latter class of materials is well known, becausethey have been used extensively in the manufacturv of demulsifiers,plasticisers, and the like. The most readily available hydroxylatedfatty body is castor oil, which consists of about 85% tr'iricinclein.One of the most suitable dibasic acids is phthalic acid, because of itslow cost, stability towards heat, etc, If triricinolein be indicated bythe following formula:

OH.R.COO.CH|

radicals are attached to adjacent carbon atoms:

coon

OOO.R.CO0.0H:

011.11.000.61; 0H.R.CoO.( )H:

coon

cooncooom noiacooca Ocoo-nooocn, I coon coon.

OOO.R.OOO.CH:

OOO.-R.COO. H

A large number of related products immediately present themselves, forinstance, esters derived by reaction with ricinoleic acid,hydroxystearic acid, dihydroxy stearic acid, and the like; or thecorresponding esters derived from glycols or glycol ethers, such asethylene glycol or diethylene glycol, which contain no free hydroxylradicals attached to the glycol radical or residue. Similarly, one mighthave products derived from monohydric alcohols, for instance, ethylricinoleate, propyl ricinoleate, sodium ricinoleate, amylaminehydroxystearate,- etc. It is intended to include blown oils. It is notthe intentio'n to include compounds of the type in which the hydroxylradical is attached to a radical or residue which replaces a carboxylichydrogen atom. For instance, it is not intended to include suchmaterials as mono-olein, di-olein, monostearin, distearin, etc.

In the examples shown above, Where the ester is polybasic, for instance,compounds of the type exemplified by C and D above, one might remove theacidity of one of the carboxylic hydrogen atoms or two of the carboxylichydrogen atoms, in any feasible manner, that is, by neutralization withan alkali or by conversion into an ester involving reaction with a newkind of an alcohol, i. e., a monohydric, dihydric, trihydric, etc.

In the case of D above, two carboxylic hydrogens may be neutralized. Inany event, however, the material derived by reaction between a polybasic acid and its functional equivalent and a hydroxylated fatty-material' of the 'kind described, is characterized by the presence ofat least one free carboxyl radical.

Where reference is made to ricinoleic acid, hydroxystearic acid,dihydroxystearic acid, a

A rial includes such hydroxy fatty acid, and the like, it is evidentthat certain simple derivatives, such as the halogenated compounds,etc., are the obvious functional equivalents; for instance, chlorinatedtriricinolein, may be employed instead of triricinolein. Brominatedricinoleic acid might be employed instead of triricinolein. Brominatedricinoleie acid might be employed instead of ricinoleic acid. In theseinstances the hydroxylated fatty material, notwithstanding modificationsof the kind indicated, still has the same functional proper-- ties asthe unmodified hydroxylated fatty material, and thus acts in the samemanner, as far as chemical reactions noted are concerned and also as faras producing an efi'ective demulsifw ing agent is '-concerned.' In thehereto appended claims reference to a hydroxylated-fatty mateobviousfunctional equivav lents.

The polybasic acids which may be employed, including some having atleast three carboxyl radicals, are 'phthalic, succinic, malic, fumaric,citric, maleic, adipic, tartaric, glutaric, diphenic, naphthalic,oxalic, etc.

As to the manufacture of materials of the kind described by reactionsinvolving the polybasic carboxy acids, or their equivalent, reference ismade to the following patents, although it is not intended to infer thatsuch patents describe these materials exclusively. However, they makesuch reference to the type of reaction involved that a. skilled chemistwould readily note the description which is particularly pertinent tothe type of material just referred to: United States Patent No.1,976,602 to De Groote, Adams and Keiser, dated October 9, 1934; andUnited States Patent No. 1,977,146, to Roberts, dated October 16, 1934.

Composition of matte1Example 1 Castor oil is reacted withtriethanolamine (see Example 1 in the previous group of intermediateamine examples) so as to produce a material corresponding to V(OELCzHg):

in which OH.R.COO represents the ricinoleic acid radical. One molecularweight of this material is reacted with three molecular weights ofdiphthalated triricinolein. See Formula C above. This is a conventionalesterification reaction, and the materials are intimately mixed andheated at approximately 120-160" C. with constant agitation, untilsamples taken from the batch and analyzed show substantially completedisappearance of the hydroxyl value. A suitable solvent may be present,and water formed may be dis tilled off continuously during theesterification process. The solvent may remain behind in the finalproduct or be removed, if desired.

Composition of matter-Example 2 The product obtained fromtriethanolamine and castor oil, as described in intermediateamine--Example 2 and corresponding to the following formula:

is reacted with diphthalated triricinolein in the same manner asindicated in Composition of matter-Example 1. i

Composition of matter-Example 3 Composition of matter--Ea:ample 4 Thesame procedure is followed as in Example 3, except that olive oil issubstituted for cocoanut oil in the manufacture of the intermediateaminea Composition of matter-Example 5 Dimaleated triricinoleinvissubstituted for diphthalated triricinolein in Composition ofmatterExarnples 1-4, inclusive.

Composition of matter-Example 6 Dicitrated triricinolein is substitutedfor diphthalated triricinolein in Composition of matter-Examples 1-4,immediately preceding.

Composition of matter-Example 7 Triphthalated triricinolein (see formulain Composition oi. matter--Example 2 above) is substituted fordiphthalated triricinolein in Composition of matter-Examples 1-4immediately preceding.

Composition of matter-Example 8 An intermediate amine is obtained byreaction between diethanolamine and castor oil, so as to yield a producthaving one non-esterlfied ethanol radical. This product is reacted withtwo moles of diphthalated triricinolein.

It should be noted that this particular product contains only twohydroxyl radicals available for esteriflcation per atom of nitrogen, andtherefore, the proper adjustment in molecular proportions, as indicated,must be made. Insofar that some amidiflcation may take place infollowing the directions in preparing the intermediate amine fromdiethanolamine, it is probably the safest procedure to determine theacetyl or hydroxyl value before reacting in molecular proportions withthe acidic ester, so as to be certain to leave a carboxyl radical.

Composition of matter-Example 9 Monophthalated hydroxystearic acid issubstituted in the various previous examples. For instance, one mayemploy two moles of monophthalated hydroxystearic acid and one mole ofthe amine product of the kind indicated in Composition of matter-Example1, above.

Composition of matter-Example 10 I Composition of matter-Example 11 Twomoles of monophthalated hydroxystearic acid and one mole of the productderived from diethanolamine and castor oil, characterized by thepresence of one non-esterified ethanol radical, are reacted in the saunamanner, as previously described.

Composition of matter-Eidmple 12 of the dihydric alcohol, as indicatedin the following manner:

(O HXCIHIE K:

As previously stated; the CzHs radical may be any one of a number ofhydrocarbon radicals which are aliphatic alicyclic, or aralkyl innature.

It is at once manifest that similar derivatives are available fromglycerols, polyglycerols, and the like, as indicated by the followingreaction:

( mlciniigljir'rmm It is not necessary to point out that the same typesof reactions will produce secondary or tertiary amines and that thereaction is not limited to a combination with ammonia, but may takeplace with a combination of other primary or secondary amines, such asamylamine, diamyla mine, cyclohexylamine, dicyclohexylamine,benzylamine,dibenzylamine, amylcyclohexylamine, etc.

This means that in the type of material previously described, there is awide variety of material, such as monoglycerylamine, diglycerylamine,monoglyceryl diethylamine,monoglyceryldipropylamine, diglycerylpropylamine, triglycerylamine, etc., which are functional equivalents ofthe various amines previously described for reaction with triricinoleinand the like. When such amines are employed instead of the radical-CnH2n appearing in a compound, one would have in place thereof theradical OH.C3H5; or, in case the hydroxyl radical of these radical hadbeen removed by esterification with any available carboxyl, then thesubstituent which replaces the CnH2n radical might be indicated by theformula --D.C3H5--. All that has been said here in regard to functionalequivalents will be perfectly obvious without further explanation tothose skilled in the art. See United States Patent No. 2,091,704, datedAugust 31, 1937, to Duncan and McAllister, and also United States PatentNo. 2,042,621, dated June 2, 1936, to Olin. Similarly, it is evidentthat where reference is made to phthalic acid, some simple derivative,such as chlorinated phthalic acid, brominated phthalic acid, methylatedphthalic acid, or the like, would simply act as a functional equivalent.This applies not only to phthalic acid, but all the dibasic acids orpolybasic acids enumerated.

Similarly, it is evident that there is no intention to differentiatebetween isomeric forms. One

. isomeric form may serve as well as another. At-

tention is particularly called to the last two examples above, which arecharacterized especially by the presence of a free carboxyl radicalother than the carboxyl radical derived from dibasic till aicassa acid.Needless to state, in the reaction between the ester derived by reactionbetween a polybasic carboxy acid-material and a selected fatty materialof the kind described, if there be a carboxyl radical attached to afatty chain available for esterification, as Well as a carboxyl attachedto the dibasic acid, then, in such event, if there is sufiicientavailable hydroxyl radicals attached to the amine of the kind previouslydescribed, both types of carboxyl radicals, i. e., (a) a .carboxylradical attached to a polybasic carboxy acid residue; and (b) a carbonylradical attached to a fatty acid residue may enter into the reaction.However, my experience is that the carbonyl radical attached to thepolybasic carboxy acid residue is generally more reactive and entersinto reaction in preference to the other type of carboxyl radical,although both reactions may take place simultaneously to at least alimited degree. I desire to emphasize that the products ob tained in theabove examples may be used in the form of the amine by direct contactwith an emulsion without contact with water. It may be contacted withwater, i. e., in the form of a solution so as to produce in a greater orlesser degree the amine base. Furthermore, any of the products abovedescribed may be combined with -a suitable acid. Acetic acid may beemployed. Hydrochloric acid is particularly desirable. In some instancesacids, such as oleic acid or naphthenic acid, may be employed to give asuitable salt. As previously pointed out, any carboxylic hydrogen atommay be replaced by a suitable metallic atom, or an organic radicalderived from an alcohol or from an amine All such ionizable hydrogenatom equivalents are considered as the functional equivalent of theionizable hydrogen atoms themselves, and such neutralized forms areincluded in the scope of the appended claims as the equivalent of theacidic form. The expres sion fatty acid compound is employed to includethe acid itself, as well as salts and esters thereof. It is realizedthat where a free carboxyl and a basic amine residue exist in the samemolecule, there may be a tendency towards the formation of inner saltscomparable to sulphanilic acid; but due to the size of the moleculeinvolved and perhaps for reasons of steric hindrance, I am not awarethat such inner salts are formed.

Briefly, then, the composition of matter herein contemplated depends ona reaction involving a polybasic carboxy acid body or its functionalequivalent, as described, and the complex amine of the kind described,in such a manner as to involve reactions other than salt formation. Inother words, the complex amines are basic in nature, and therefore,could react with a polybasic acid to form a salt in a manner which, forsake of convenience, will be indicated by a somewhat simpler reaction,thus:

coon

(R):N+T ammo 01120 0 on on C0 or Rmmoocmcoom Such reactions are purelysalt formation. The materials of the kind herein contemplated,regardless of their nature, are of the kind obtained by reactions otherthan salt formation, and also other than amidlfication.

I desire to emphasize that the expression polybasic carboxy acid, as itappears in the claims, refers not only to the acid itself, but to anyfunctional equivalent, such as the anhydride, the acyl chloride, a saltform having at least two free carboxyls, such as mono-sodium citrate,etc. It is also understood that in the hereto appended claims the natureof the final product is not limited to the form having a free carboxylichydrogen, but that such free carboxylic hydrogen may actually bereplaced by any functional equivalent of the kind previously described,for

instance, a metallic atom, an ammonium radical,

an amine radical, such as an amylamine radical, benzylamine radical,ethanolamine radical, diethanolamine radical, triethanolamine radical, ahydrocarbon radical, such as an ethyl, methyl, propyl, or amyl radical,a radical derived from ethylene glycol, glycerol, or the like; acyclohexyl radical, benzyl radical, etc. All such forms in which suchionizable hydrogen atom equivalent involving the replacement of an aminohydrogen atom by an acyl radical without conventional limitation to areaction involving ammonia. The replacement of the amino hydrogen atom'of a primary amine or a secondary amine by an acyl radical has beenconsidered as being amidification, rather than the formation of asubstituted amide or the formation of an imide or substituted imide.Such obvious departure. from con-- ventional nomenclature has been forpurposes of simplicity and to show the similarity between certainreactions.

It is desirable to emphasize again that in the hereto appended claimsreference to a. polybaslc carboxy acid compound includes not only theacid itself, but also various salts and esters thereof, and also otherfunctional equivalents, such as the anhydrides, acyl chlorides, etc.Similarly, in the hereto appended claims reference to a hydroxylatedfatty acid compound includes not only the fatty acid itself, but alsothe salts and esters thereof, except esters of the kind in which thereis a hydroxyl attached to the hydrocarbon radical derived irom theesterifying alcohol; i. e., it is not intended to include esters such asmonoricinolein, diricinolein, etc., characterized by the presence of ahydroxyl radical attached to the organicradical which replaces theionizable hydrogen atom of the carboxy radical of the fatty acid.Furthermore, in the heretoappendcd claims, reference to the productderived by reaction between an acid ester of the kind previouslydescribed and an amine of the kind previously described, is meant torefer to such products in all its various modifications previouslyreferred to, to wit, such instances where carboxylic' hydrogen atomsappear as such or have been replaced by metallic atoms, organic radicalsderived from various alcohols, amine radicals, or residues, etc.; and asto the presence of any basic amine nitrogen atom, it'

may be in the amine form or in a. salt form or in a base form, as, forexample, obtainable by contact with water. The functional equivalents ofall these variations have been pointed out previously and were readilycomprehended; and the scope of the claims, in light of such obviousequivalents, requires nofurther discussion;

As to blown oils, blown fatty acids, polymerized oils, polymerized fattyacids, and other similar materials obtained byoxidation, it.isunderstood that they may be reacted with the polybasic carboxy acids,such as phthalic acid or phthalic anhydride to produce an acidic ester;but it is not intended. that they should be reacted with amines toproduce the intermediate amine, which in ethyl alcohol, denaturedalcohol, propyl alcohol,

butyl alcohol, hexyl alcohol, octyl alcohol, etc.,

maybe employed as diluents. Miscellaneous solvents, such as pine oil,carbon tetrachloride, sulfurdioxide extract obtained in the refining ofpetroleum, etc., may be employed as diluents. Similarly, the material ormaterials employed as the demulsifying agent of my process may beadmixed with one or more of the solvents customarily used in connectionwith conventional V demulsifying agents. Moreover, said material orsolubility.

materials may be used alone or in admixture with other suitable. wellknown classes of demulsifying agents.

It is well known that conventional demulsii'ying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oil and water solubility. Sometimes they may be used in a formwhich exhibits relatively limited water solubility and relativelylimited 011 However, since such reagents are sometimes used in a ratiooi. 1 to 10,000 or 1 to 20,000, or even 1 to 30,000, such an apparentinsolubility in 'oil and water is not significant, be-

cause said reagents undoubtedly have solubility within the concentrationemployed. This same fact is true in regard to the material or materialsemployed as the demulsitying agent of, my process.

I desire to point out that the superiority of the reagent ordemulsifying agent contemplated in mrproeess is based upon its abilityto treat certain emulsions .more advantageously and at a somewhat lowercost than is possiblewith other available'demulsifiers, or conventionalmixtures thereof. It is believed that the particular demulsifying agentor treating agent herein described will find comparatively limitedapplication, so far as the majority or oil field emulsions areconcerned; but I have found that such a demo]- sii'ying agent hascommercial value, as it will economically break or resolve oil fieldemulsions in a number'of cases which cannot be treated as easily or atso low a costwith the demulsifying agents heretofore available.

In practising my process, a treating agent or demulsitying agent of thekind above described is brought into contact. with or caused to act uponthe emulsion to be treated, in any of the various ways or by any of thevarious apparatus now gener'ally used to resolve or break petroleumemulsions with a chemical reagent, the above procedure being used eitheralone or in combination with other demulsifyin'g procedure, such as theelectrical dehydration process.

The new composition or matter that is employed as the demulsii'yingagent' in my process herein described constitutes the subject-matter ofmy pending application for Patent Serial No. 261,092, filed March 10,1939.

Having thus described my invention, what I claim and desire to secure byLetters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type.characterized by subacid having not more than 32 carbon atoms; T

represents a hydrogen atom or a non-hydroxy hydrocarbon radical or theacylated radical derived by replacing a hydrogen atom of the hy-. droxylgroup of an alkylol radical by the acyl radical of a monobasic carboxyacid having less than 8 carbon atoms; n represents a small whole numberwhich is less than 10; m represents the munber 1 or 2; m represents thenumber 1 or 2,

and m" represents the number 0 or 1, with the proviso that m+m-i -m"=3;and (B) an acidic ester derived by reaction between a polybasic carboxyacid and a hydroxylated fatty acid com- -'pound; said fatty acidcompound being characterized by the absence of any hydroxy hydrocarbonradicalas a substituent'for the hydrogen atom in the carboxyl part ofthe hydroxy fatty acid radical; saldacidic ester being characterized bythe presence of at leastone carboxyl radical.

2. A process tor breaking petroleum emulsions of the water-in-oil type.characterized by subjecting the emulsion to the action ota'demulsii'ying agent comprising products of the kind derivablebyesterification reaction between (A) an amine or the formula type12,000.03...)

(OILCHHa) in which R1300 represents the oxy-acyl radical derived from adetergent-forming monocarboxy acid having not more than 32 carbon atoms;and n is a small whole number less than 10; and (B) an acidic esterderived by reaction between a polybasic carboxy acid and a hydroxylatedfatty acid compound; said fatty acid compound being characterized by theabsence or any hydroxy hydrocarbon radical as a substituent tor thehydrogen atom in the carboxyl part of the hydroxy fatty acid radical;said acidic ester being characterized by the presence of at least onecar' boxyl radical.

3. A process for breaking petroleum emulsions of the water in-oil type,characterized by subjecting the emulsion to the action of ademulsityagent comprising productsof thekind derivable by esteriflcationreaction between (A) an amine of the formula type derived from adetergent-forming monocarboxy 7 acid having not more than 32 carbonatoms; 1:

represents a small whole number which is less than 10; m represents thenumber 1 or 2;"m' represents thev number 1 or 2, with the proviso thatm+m'=3; and (B) an acidic ester derived by reaction between a polybasiccarboxy acid and a hydroxylated fatty acid compound; said fatty acidcompound being characterized by the absence of any hydroxy hydrocarbonradical as a substituent for the hydrogen atom in the carboxyl amenaapart of the hydroxy fatty acid radical; said acidic ester beingcharacterized by the presence of at least one carboxyl radical.

4. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of ade1nulsifying agent comprising products of the kind derivable byesterification reaction between (A) an amine of the formula type.

(R.OOO.C2H4)2 N (OH.C2H4)/ in which R1300 is an oxy-acyl radical derivedfrom a fatty acid; and (B) an acidic ester derived by reaction between apolybasic car-boxy acid and a hydroxylated fatty acid compound; saidfatty acid compound being characterized by the absence of any hydroxyhydrocarbon radical as a substituent for the hydrogen atom in thecarboxyl part of the hydroxy fatty acid radical; said acidic ester beingcharacterized by the presence of at least one carboxyl radical.

5. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising products of the kind derivable by esterificationreaction between (A) an amine of the formula type in which R.COO is anoxy-acyl radical derived from a fatty acid; and (B) an acidic esterderived by reaction between a polybasic carboxy acid and a hydroxylatedfatty acid compound; said fatty in which R.COO is an oxy-acyl radicalderived from a fatty acid; and (B) an acidic ester derived by reactionbetween phthalic anhydride and tri ricinolein; said ester beingcharacterized by the presence of at least one free carboxyl radical.

l. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising products of the kind derivable by esterificationreaction between (A) an amine of the formula type in which R.COO is anoxy-acyl radical derived from a fatty acid; and (B) an acidic esterderived by reaction between phthalic anhydride and triricinolein; saidester being characterized by the presence of at least one free carboxylradical.

MELVIN DE GROOTE.

